Polymer additives, their manufacturing methods, and applications

Abstract

The present invention provides a polymer additive that exhibits excellent heat resistance and stability, and significantly reduces corrosion of metal processed parts in metal-based production equipment when used in the flame-retardant modification process. [Solution] The polymer additive contains aluminum diethylphosphinate having the structural formula shown in formula (I) below and aluminum ethylbutylphosphinate having the structural formula shown in formula (II) below, satisfying the dual enthalpy ratio ΔH: 0.92 ≤ ΔH ≤ 1.06 as defined by formula ΔH = H2 / H1, and also satisfying 130℃ ≤ T1 ≤ 155℃ and 165℃ ≤ T2 ≤ 185℃. JPEG2026109605000007.jpg37128

Description

Technical Field

[0001] The present invention belongs to the technical field of flame retardants, and more specifically, relates to polymer additives, their manufacturing methods, and applications.

Background Art

[0002] Aluminum diethylphosphinate is a halogen-free and environmentally friendly flame retardant. It has a white powder appearance, is insoluble in water and most organic solvents, but is soluble in strong acid and strong alkali solutions. It has characteristics such as high flame retardancy, high thermal stability, low smoke, small particle size, low specific gravity, excellent dispersibility, and compatibility. Aluminum diethylphosphinate is widely used as an efficient and environmentally friendly halogen-free flame retardant for flame retardant treatment of products such as thermoplastic plastics (PPA, PA66, PBT, etc.), fibers, and fabrics.

[0003] Composite systems of aluminum diethylphosphinate are widely used in the field of halogen-free flame-retardant glass fiber reinforced engineering plastics. Such composite systems include, for example, aluminum diethylphosphinate - melamine polyphosphate (MPP) composite system, aluminum diethylphosphinate - melamine cyanurate (MCA) composite system, and aluminum diethylphosphinate - aluminum phosphite composite system, etc. These systems have advantages such as high flame retardant efficiency, high temperature resistance, and little performance degradation of the resin matrix, so they are widely used.

[0004] Conventional aluminum diethylphosphinate has a high heat resistance temperature. In most of the quality manuals of commercial products, it is required that the 1wt% thermogravimetric reduction temperature is 350°C or higher (nitrogen atmosphere, 20°C / min). However, corrosion of the screw during the flame retardant treatment of modified engineering plastics (PBT, PA, etc.), especially special engineering plastics (such as high-temperature nylon), is still serious, and improvement by synergistic action with some additives is necessary.

[0005] Currently, the thermal decomposition and flame retardant mechanisms of aluminum diethylphosphinate are being studied in related literature. It has been found that during the decomposition process of aluminum diethylphosphinate, acidic substances such as diethylphosphinic acid produced volatilize into the gas phase, are completely decomposed into phosphorus atoms, and further form a phosphorus-containing free radical quencher, thereby performing a gas-phase flame retardant effect. Chinese patent CN107189098A discloses a polymer additive formulated in combination with aluminum diethylphosphinate and / or alkylaluminum phosphite. This additive can significantly reduce corrosion to screws while minimizing the impact on the color of the polymer itself. Chinese patent CN110407869A discloses a monotrifluoropropylphosphinate flame retardant that, by formulating monotrifluoropropylphosphinate and aluminum diethylphosphinate in combination, can reduce the corrosiveness of aluminum diethylphosphinate to screws during the extrusion modification process.

[0006] However, the above solution improves the corrosiveness of aluminum diethylphosphinate by combining it with other components, but serious corrosion problems due to aluminum diethylphosphinate still exist during the screw extrusion process. Therefore, providing aluminum diethylphosphinate with lower corrosiveness is an urgent technical challenge that must be addressed. [Overview of the project]

[0007] In view of the above-mentioned conventional technical problems, the object of the present invention is to provide a polymer additive that has excellent heat resistance and stability, and significantly reduces corrosion of metal processed parts of metal production equipment when used in a flame retardant modification process.

[0008] To achieve the above objective, the present invention is realized by the following technical solutions.

[0009] In the first embodiment, the polymer additive according to the present invention comprises aluminum diethylphosphinate having the structural formula shown in the following formula (I) and aluminum ethylbutylphosphinate having the structural formula shown in the following formula (II). JPEG2026109605000001.jpg36128 The polymer additive satisfies the dual enthalpy ratio ΔH defined by the following formula (1) ΔH: 0.92 ≤ ΔH ≤ 1.06, and also satisfies 130℃ ≤ T1 ≤ 155℃ and 165℃ ≤ T2 ≤ 185℃. ΔH = H2 / H1 (1) H1, H2, T1, and T2 were measured by differential scanning calorimetry (DSC), and the measurement method included heating the polymer additive from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min in a nitrogen atmosphere, maintaining this temperature for 3 minutes, then cooling it down to room temperature at a further rate of 20°C / min to obtain the cooling curve of the polymer additive, maintaining the polymer additive at room temperature for 3 minutes, and then heating it again to a maximum temperature of 300°C at a heating rate of 20°C / min to obtain the second heating curve of the polymer additive. H1 is the peak area formed by the start and end temperatures of the exothermic peak in the cooling curve, and T1 is the peak temperature of the exothermic peak in the cooling curve. H2 is the peak area formed by the start and end temperatures of the endothermic peak in the second heating curve, and T2 is the peak temperature of the endothermic peak in the second heating curve.

[0010] Differential scanning calorimetry (DSC) is used to represent the melting and crystallization processes of polymers and can reflect the relationship between polymer structure and crystals. Changes in polymer structure directly determine the melting and crystallization behavior during heating or cooling in DSC measurements. The practical physical meaning reflected by the dual enthalpy ratio ΔH is the relationship between the polymer's crystal structure fracture, the difficulty of crystallization, and the polymer structure. Crystallization behavior is closely related to the crystal's melting behavior and structural properties. When there are significant differences in polymer structure, large changes occur in the crystallization behavior of polymer molecular chains and arrangements, and the fracture behavior of the crystal structure, which are reflected by the fact that the ratio of melting enthalpy to crystallization enthalpy (i.e., the dual enthalpy ratio) in DSC exhibits a certain degree of variability. This variation in the dual enthalpy ratio reflects the structural properties of the polymer and the resulting changes in the polymer's macroscopic thermal stability.

[0011] Through their research, the inventors discovered that, given a specific dual enthalpy ratio, T1 and T2, the polymer additive possesses a particular structure. This structure makes the polymer additive less susceptible to destruction of its crystalline structure and morphology during heating, resulting in superior thermal stability, suppressed decomposition during processing, and significantly reduced corrosion of metal processed parts (such as screws) in metal-based production equipment.

[0012] Specifically, in some embodiments, the peak areas H1, H2 and peak temperatures T1, T2 may be obtained by peak marking and integral calculation of peak areas using conventional methods in the art. For example, they may be obtained by performing peak marking and integral calculation of peak areas using software attached to a DSC instrument. Specifically, in some embodiments, when measured by differential scanning calorimetry (DSC), the weight of the sample of polymer additive to be measured may be 10 ± 0.5 mg.

[0013] Specifically, in some embodiments, peak areas H1, H2 and peak temperatures T1, T2 can be obtained as average values ​​after multiple integrations or markings (e.g., 1, 2, 3, 4, 5 times, etc.). More specifically, from the viewpoint of improving operational efficiency and ensuring data reproducibility and reliability, peak areas H1, H2 and peak temperatures T1, T2 can each be measured independently 2 to 4 times and obtained as average values.

[0014] In some embodiments, the polymer additive comprises, by weight percentage, 97.01% to 98.99% aluminum diethylphosphinate and 1.01% to 2.99% aluminum ethylbutylphosphinate. More specifically, the content of aluminum diethylphosphinate may be 97.30%, 97.50%, 97.70%, 97.90%, 98.10%, 98.30%, 98.50%, 98.70%, 98.90%, etc., or within a numerical range formed from any of the above values, such as 97.01 to 97.70%, 97.30 to 97.90%, 97.01 to 98.30%, 98.10 to 98.50%, 98.90 to 98.99%, 98.50 to 98.90%, but the present invention is not limited to these. More specifically, the content of aluminum ethylbutylphosphinate may be 1.20%, 1.40%, 1.60%, 1.80%, 2.00%, 2.20%, 2.40%, 2.60%, 2.80%, 2.90%, or within a numerical range formed from any of the above values, such as 1.01-2.50%, 1.01-2.20%, 1.10-2.20%, 1.40-2.20%, 1.80-2.60%, but the present invention is not limited to these.

[0015] In some embodiments, the polymer additive satisfies the dual enthalpy ratio ΔH: 0.93 ≤ ΔH ≤ 1.05, and also satisfies the temperature ranges of 132°C ≤ T1 ≤ 153°C and 170°C ≤ T2 ≤ 183°C.

[0016] More specifically, the dual enthalpy ratio ΔH of the present invention may be 0.93, 0.94, 0.96, 0.98, 1.00, 1.02, 1.04, etc., or within a numerical range formed from any of the above values ​​such as 0.95 to 1.02, 0.96 to 1.00, but the present invention is not limited to these.

[0017] The T1 of the present invention may be 130°C, 132°C, 134°C, 136°C, 138°C, 140°C, 142°C, 144°C, 146°C, 148°C, 150°C, 152°C, 154°C, 155°C, etc., or it may be within a numerical range formed from any of the above values, such as 134°C to 142°C or 140°C to 154°C, but the present invention is not limited to these.

[0018] The T2 of the present invention may be 165°C, 167°C, 169°C, 171°C, 173°C, 175°C, 177°C, 179°C, 181°C, 183°C, 185°C, etc., or it may be within a numerical range formed from any of the above values, such as 167°C to 175°C or 171°C to 177°C, but the present invention is not limited to these.

[0019] More preferably, the polymer additive satisfies a dual enthalpy ratio ΔH: 0.92 ≤ ΔH ≤ 0.93, and satisfies 146°C ≤ T1 ≤ 148°C and 178°C ≤ T2 ≤ 180°C. If it is within this preferred range, the polymer additive has better thermal stability and less corrosion to the screw during the extrusion modification process.

[0020] In some embodiments, the water content of the polymer additive is 0.05% to 0.40 wt%.

[0021] In some embodiments, the bulk density of the polymer additive is 150 to 800 g / L, preferably 350 to 750 g / L.

[0022] In some embodiments, the water solubility of the polymer additive is 0.01 to 5 g / L.

[0023] In a second aspect, the present invention introduces a water-soluble salt or acid of hypophosphorous acid and an initiator into a jet loop reaction system, and reacts with an olefin so that 2.00 to 2.05 molecules of olefin are added to the P atom in one water-soluble salt or acid of hypophosphorous acid itself to obtain an intermediate aqueous solution containing diethyl phosphate (step (a)); performing a metathesis reaction on the intermediate aqueous solution with a water-soluble aluminum salt to obtain a polymer additive (step (b)); and provides a method for producing a polymer additive including the above steps.

[0024] In the above embodiment, in step (a), the pressure of the olefin in the jet loop reaction system is 0.3 to 3.0 MPa.

[0025] In the above embodiment, in step (a), the reaction temperature in the jet loop reaction system is 70 to 150 °C.

[0026] More preferably, in some embodiments, the pressure of the olefin in the jet loop reaction system is 1.2 to 1.6 MPa, and the reaction temperature in the jet loop reaction system is 100 to 110 °C.

[0027] In the above embodiment, in step (b), the mass concentration of diethyl phosphate in the intermediate aqueous solution is 20 to 25%.

[0028] In the above embodiment, the mass concentration of the water-soluble aluminum salt in the water-soluble aluminum salt solution is 20 to 25%.

[0029] In the above embodiment, in step (b), the pH of the metathesis reaction is 3.0 to 3.1.

[0030] In the above embodiment, in step (b), the temperature of the metathesis reaction is 40 to 45 °C.

[0031] In the above embodiment, in step (b), the molar ratio of diethylphosphinate to aluminum ions in the water-soluble aluminum salt is 3:(1~1.01).

[0032] In the above embodiment, the jet loop reaction system comprises at least one set of jet loop reactors and 0 to 3 aging reactors. Alternatively, the jet loop reaction system may consist of one set of intermittent jet loop reactors without aging reactors. If the jet loop reaction system includes multiple sets of continuous jet loop reactors, each of the multiple sets of jet loop reactors is connected in parallel or in series with an aging reactor.

[0033] In the above embodiment, the jet loop reactor may be a reactor with a stirring function or a jet loop reactor without a stirring function. The aging reactor may be an autoclave, a jet loop reactor, a stepped column, a bubble column, a falling membrane reactor, etc.

[0034] In the above embodiment, when mixing the intermediate aqueous solution and the water-soluble aluminum salt, the intermediate aqueous solution may be added dropwise to the water-soluble aluminum salt, or the intermediate aqueous solution and the water-soluble aluminum salt may be added dropwise to the reactor simultaneously.

[0035] In a third aspect, the present invention relates to a method for producing another polymer additive, (a) A water-soluble salt or acid of hypophosphorous acid is reacted with an olefin at 90-100°C in the presence of an initiator, under the protection of a nitrogen gas atmosphere, such that 2.00 to 2.05 molecules of olefin are added to one P atom in the water-soluble salt or acid of hypophosphorous acid itself, and the temperature is maintained to obtain an intermediate aqueous solution containing diethylphosphinate. (b) The intermediate aqueous solution and the water-soluble aluminum salt are mixed and reacted at ≤15°C while stirring, and the temperature is further raised to 70-95°C and maintained to obtain a polymer additive. The present invention provides a manufacturing method that includes the following:

[0036] In the above embodiment, step (a) involves maintaining the temperature in two stages, with the first temperature maintenance period being 3.5 to 4.5 hours, during which the initiator is continuously replenished, and then the temperature is maintained for another 0.5 to 1.5 hours.

[0037] In the above embodiment, in step (b), the mixture is mixed and reacted at 0 to 10°C.

[0038] In the above embodiment, the pH of the reaction in step (b) is 3.0 to 7.0.

[0039] In the above embodiment, in step (b), a water-soluble aluminum salt is added dropwise to the intermediate aqueous solution while stirring, mixed, and reacted for 1.5 to 2.5 hours.

[0040] In the above embodiment, in step (b), the rate of heating is 2 to 15°C / hour.

[0041] In the above embodiment, the time for maintaining the temperature in step (b) is 5 to 30 minutes.

[0042] In the above embodiment, in step (b), the molar ratio of diethylphosphinate to aluminum ions in the water-soluble aluminum salt is 3:(1~1.01).

[0043] In a fourth aspect, the present invention relates to a method for producing another polymer additive, Step (a) involves reacting hypophosphorous acid with an olefin at 90-100°C under the protection of a nitrogen gas atmosphere, in the presence of an initiator, such that 2.00 to 2.05 molecules of olefin are added to the P atom in one hypophosphorous acid molecule, maintaining the temperature to obtain an intermediate aqueous solution containing diethylphosphinic acid. Step (b) for producing an aluminum hydroxide gel solution, Step (c) involves adding an intermediate aqueous solution dropwise into an aluminum hydroxide gel solution and allowing it to react, raising the temperature to 90-120°C, and maintaining the temperature for 0.1-5 hours to obtain a polymer additive. The present invention provides a manufacturing method that includes the following:

[0044] In the above embodiment, step (a) involves maintaining the temperature in two stages, with the first stage lasting 2.5 to 3.5 hours, during which the initiator is continuously replenished, and then the temperature is maintained for another 1.5 to 2.5 hours.

[0045] In the above embodiment, during the temperature maintenance process of step (a), a portion of the reactants in the reactor is introduced into the venturi ejector, thoroughly mixed with the ethylene introduced into the venturi ejector, and then returned to the reactor via external circulation.

[0046] In the above embodiment, in step (b), an aqueous sodium hydroxide solution is added dropwise to an aqueous aluminum sulfate solution to obtain an aluminum hydroxide gel solution.

[0047] In the above embodiment, the temperature at the time of dropping in step (b) is 10 to 20°C.

[0048] In the above embodiment, in step (c), the rate of heating is 2 to 25°C / hour.

[0049] In the above embodiment, in step (c), the molar ratio of diethylphosphinic acid to aluminum ions in the aluminum hydroxide gel solution is 3:(1~1.01).

[0050] In some embodiments, the initiator is one or more selected from the group consisting of organic peroxides, inorganic peroxides, and azo compounds. More specifically, the inorganic peroxide may be one or more selected from the group consisting of sodium persulfate, ammonium persulfate, and potassium persulfate. The organic peroxide may be one or more selected from the group consisting of perbenzoic acid, perlauric acid, di-tert-butyl peroxide, percarbonate ester, peracetic acid, tert-butyl peroxyisobutyrate, and tert-butyl peroxypivalate. The azo compound may be one or more selected from the group consisting of azobisisobutyronitrile and azobisisoheptanitrile.

[0051] In some embodiments, the olefin may be at least one of ethylene, propene, 1-butylene, 2-butylene, 1-pentene, 1-hexene, and 1-octene.

[0052] In some embodiments, the water-soluble salt of hypophosphate may be potassium hypophosphate and / or sodium hypophosphate.

[0053] In some embodiments, the water-soluble aluminum salt may be one or more selected from the group consisting of aluminum oxides, hydroxides, peroxides, sulfates, bisulfates, hydrated sulfates, persulfates, phosphates, and phosphites.

[0054] Furthermore, the present invention seeks protection for the use of the polymer additive in reducing corrosion in metal-based production equipment. In particular, it seeks protection for the use of the polymer additive in reducing corrosion in metal parts such as screws in metal-based production equipment.

[0055] Furthermore, the present invention provides for the use of polymer additives as reactive or non-reactive flame retardants in polymers, varnishes, foaming paints, wood and other cellulose-containing products, for the use of the polymer additives in the manufacture of flame-retardant polymer molding materials and / or flame-retardant polymer molded articles, and for imparting flame retardancy to polyester fabrics and / or pure cellulose fabrics and / or blended cellulose fabrics by impregnation.

[0056] Furthermore, the polymer additive is used in combination with a synergistic agent, the synergistic agent being one or more selected from the group consisting of melamine phosphate, di(melamine) phosphate, penta(melamine) triphosphate, tri(melamine) diphosphate, tetra(melamine) triphosphate, hexa(melamine) pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, and melon polyphosphate, or the synergistic agent being melam, melem, and / or melon, which are melamine condensation products, or the synergistic agent being one or more selected from the group consisting of oligoesters of tri(hydroxyethyl) isocyanurate / salt and aromatic polycarboxylic acid, benzoguanamine, tri(hydroxyethyl) isocyanurate / salt, allantoin, glycoluryl, melamine, melamine cyanurate, urea cyanurate, dicyandiamide, and guanidine, or the synergistic agent being of formula (NH4) y H 3-y PO4 and / or (NH4PO3) zThe synergistic agent is a nitrogen-containing phosphate represented by the formula (wherein y is 1 to 3 and z is 1 to 10000), or the synergistic agent is aluminum phosphite and / or aluminum pyrosphite, or the synergistic agent is one or more selected from the group consisting of zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, and magnesium carbonate, or the synergistic agent is one or more selected from the group consisting of salts of ethylphosphonic acid, salts of butylphosphonic acid, salts of n-butylphosphonic acid, salts of sec-butylphosphonic acid, and salts of hexylphosphonic acid.

[0057] Furthermore, the polymer additive is used in combination with other additives, the other additive being at least one selected from the group consisting of antioxidants, UV stabilizers, gamma-ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact resistance modifiers, dyes, and pigments.

[0058] Furthermore, the polymer additive is used in an amount of 0.0001 to 99.7999% by weight, a synergistic agent in an amount of 0.1 to 40% by weight, and other additives in an amount of 0.1 to 40% by weight.

[0059] In a fifth aspect, the present invention claims protection for a flame-retardant thermoplastic or thermosetting polymer composite material comprising 0.5 to 45% by weight of the polymer additive, 0.5 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of a synergistic agent, and 0 to 55% by weight of a filler or reinforcing material.

[0060] In some embodiments, the thermoplastic or thermosetting polymer is one or more selected from the group consisting of polyester, polyamide, thermoplastic elastomer, thermoplastic polyurethane, thermoplastic polyester elastomer, styrene-based polymer, polyketone, polyolefin, and polyacrylate.

[0061] In some embodiments, the flame-retardant thermoplastic or thermosetting polymer composite material may be a flame-retardant thermoplastic or thermosetting polymer molding material, a flame-retardant thermoplastic or thermosetting polymer molded article, a flame-retardant thermoplastic or thermosetting polymer film, a flame-retardant thermoplastic or thermosetting polymer yarn, or a flame-retardant thermoplastic or thermosetting polymer fiber.

[0062] In some embodiments, the polyolefin may be a polymer of monoenes and / or dienes such as polypropylene, polyisobutylene, poly-1-butylene, poly-4-methyl-1-pentene, polyisoprene, or polybutadiene, or the polyolefin may be a polymer of cycloolefins such as cyclopentene or norbornene. Specifically, the polyolefin may be polyethylene (crosslinkable as needed), such as high-density polyethylene (HDPE), high-density-high molecular weight polyethylene (HDPE-HMW), high-density-ultra-high molecular weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), and mixtures thereof.

[0063] Polyolefins may also be copolymers of monoenes and dienes, or copolymers of other ethylenic monomers, such as ethylene-propylene copolymers, copolymers of linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE), propylene-1-butylene copolymers, propylene-isobutylene copolymers, ethylene-1-butylene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and copolymers thereof with carbon monoxide, ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene, propylene, and dienes (e.g., hexadiene, dicyclopentadiene, or ethylidene norbornene). Furthermore, the polyolefin may be a mixture of the aforementioned polymers or copolymers, for example, polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer, LDPE / ethylene-acrylic acid copolymer, LLDPE / ethylene-vinyl acetate copolymer, LLDPE / ethylene-acrylic acid copolymer, and alternating or statistically configured polyalkylene / carbon monoxide copolymer. Alternatively, the polyolefin may be a mixture of the aforementioned polymers or copolymers with other polymers such as polyamides.

[0064] In some embodiments, the styrene-based polymer may be a copolymer of styrene or α-methylstyrene with a diene or acrylic acid derivative, such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-alkyl methacrylate copolymer, styrene-butadiene-alkyl acrylate copolymer, styrene-butadiene-alkyl methacrylate copolymer, styrene-maleic anhydride copolymer, or styrene-acrylonitrile-methyl acrylate copolymer. Alternatively, the styrene-based polymer may be a high-impact mixture of the styrene copolymer and another polymer (e.g., polyacrylate, a diene polymer, or an ethylene-propylene-diene ternary copolymer). Furthermore, the styrene-based polymer may be a block copolymer of styrene, such as styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, or styrene-ethylene / propylene-styrene block copolymer.

[0065] In some embodiments, the styrene-based polymer may be a graft copolymer of styrene or α-methylstyrene, or a mixture thereof. For example, the styrene-based polymer may be a graft copolymer in which styrene is grafted onto polybutadiene, a graft copolymer in which styrene is grafted onto polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer, a graft copolymer in which styrene and acrylonitrile (or methylacrylonitrile) are grafted onto polybutadiene, a graft copolymer in which styrene, acrylonitrile and methyl methacrylate are grafted onto polybutadiene, a graft copolymer in which styrene and maleic anhydride are grafted onto polybutadiene, a graft copolymer in which styrene, acrylonitrile and maleic anhydride or maleimide are grafted onto polybutadiene, These may be graft copolymers in which styrene and alkyl acrylate or alkyl methacrylate are grafted onto polybutadiene, graft copolymers in which styrene and acrylonitrile are grafted onto ethylene-propylene-diene ternary copolymer, graft copolymers in which styrene and acrylonitrile are grafted onto polyalkyl acrylate or polyalkyl methacrylate, graft copolymers in which styrene and acrylonitrile are grafted onto acrylate-butadiene copolymer, acrylonitrile-butadiene-styrene (ABS) polymer, methyl methacrylate-butadiene-styrene (MBS) polymer, acrylonitrile-styrene-butyl acrylate (ASA) polymer, or acrylonitrile-ethylene-styrene (AES) polymer.

[0066] In some embodiments, the polyamide may be (1) a polyamide or copolyamide derived from a diamine and a dicarboxylic acid, and / or (2) a polyamide or copolyamide derived from an aminocarboxylic acid and a corresponding lactam, for example, polycaprolactam (PA6), poly(hexamethyleneadipamide) (PA66), and polytetramethyleneadipamide (polyamide 46 or PA46). Furthermore, the polyamide may be an aromatic polyamide derived from m-xylene, diamine, and adipic acid, or a polyamide produced from hexamethylenediamine, isophthalic acid and / or terephthalic acid, and an elastomer as an optional modifier (e.g., poly(hexamethylene isophthalamide), poly(hexamethylene teraphthalamide), poly-2,4,4-trimethylhexamethylene terephthalamide, or poly(m-phenylene isophthalamide)). The polyamide may also be a block copolymer of a polyamide with a polyolefin, olefin copolymer, ionomer, or chemically bonded or grafted elastomer, or a block copolymer of a polyamide with a polyether such as polyethylene glycol, polypropylene glycol, or polybutylene glycol.

[0067] In some embodiments, the polyester may be a polyester derived from dicarboxylic acids and diols, and / or from hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dihydroxymethylcyclohexane terephthalate, and polyhydroxybenzoic acid esters. Alternatively, the polyester may be a block polyether ester derived from a polyether containing a hydroxy-terminated group, or a polyester modified from polycarbonate or methyl butadiene styrene ternary copolymer (MBS).

[0068] In some embodiments, the filler or reinforcing material may be (1) a silicon-oxygen-containing compound, (2) a compound of a metal in Group 2 of the periodic table, specifically a magnesium compound such as magnesium oxide, magnesium hydroxide, hydrotalcite, dihydrotalcite, magnesium carbonate or magnesium calcium carbonate, or a calcium compound such as calcium hydroxide, calcium oxide or hydrocalmite, (3) an aluminum compound such as aluminum oxide, aluminum hydroxide, boehmite, gibbsite or aluminum phosphate, and / or (4) red phosphorus, a zinc compound, or glass fiber.

[0069] Compared to the prior art, the present invention has the following beneficial effects.

[0070] The polymer additive according to the present invention has a specific crystal structure and morphology due to the dual enthalpy ratio ΔH and T1 and T2 being within a specific range, resulting in superior thermal stability, reduced decomposition during processing, and reduced corrosion of metal processed parts in metal-based production equipment. [Modes for carrying out the invention]

[0071] The present invention will be further described below with reference to specific examples, but these examples are not intended to limit the present invention. Unless otherwise specified, the reagents, methods, and apparatus used in the present invention are common reagents, methods, and apparatus in the art.

[0072] The raw materials for the examples and comparative examples are as follows: Sodium hypophosphate monohydrate: Commercially available product. Sodium persulfate: Commercially available product. Aluminum sulfate 18-hydrate: Commercially available product. Glass fiber: ECS10-03-568H, purchased from China Jushi Co., Ltd. Melamine polyphosphate: BUDIT3141, purchased from BASF Europe. Base resin 1: PA66, EPR24, purchased from Henan Shenma Nylon Chemical Co., Ltd., China. Base resin 2: PA6, M2000, purchased from Hengshen Meida New Materials Co., Ltd., Guangdong, China. Base resin 3: PBT, GX121, purchased from China Petrochemical Instruments & Chemical Fibers Co., Ltd. Unless otherwise specified, all components used in each parallel example and comparative example are the same commercially available products.

[0073] Example 1 (1) Preparation of an intermediate aqueous solution containing sodium diethylphosphinate. The specific procedure was as follows: (i) An aqueous solution of sodium hypophosphite monohydrate (35% mass concentration of sodium hypophosphite in the aqueous solution), an aqueous solution of sodium persulfate as an initiator (20% mass concentration of sodium persulfate in the aqueous solution), and ethylene were added to the first jet loop reactor (1000 L). The ethylene pressure in the first jet loop reactor was controlled to 1.6 MPa and the temperature to 105 °C, and the reaction was carried out continuously. After the continuous reaction, the substances in the first jet loop reactor were added to the second jet loop reactor (2000 L) and the reaction was carried out continuously. Simultaneously, the initiator and ethylene were replenished in the second jet loop reactor, and the ethylene pressure in the second jet loop reactor was controlled to 1.2 MPa and the temperature to 100 °C. The discharge space velocity of the jet loop reactor system was set to 0.2 / hour. (ii) After the reaction, the substances in the second jet loop reactor were each placed into two parallel aging vessels (5000 L), and at the same time, initiators and ethylene were added to the aging vessels, and the ethylene pressure in the two aging vessels was set to 1.0 MPa and the temperature to 95°C. (iii) The supply rate of the sodium hypophosphate monohydrate aqueous solution was 300 kg / hour, and the total supply rate of the sodium persulfate aqueous solution was 23 kg / hour. The sodium persulfate aqueous solution was distributed in the first jet loop reactor: second jet loop reactor: two aging vessels in a mass ratio of 3:1:0.3:0.3. The rate and pressure of ethylene entering the reactors were maintained by control valves, and the pressure and temperature of each reactor were maintained. After aging in the aging vessels, when the ethylene pressure no longer decreased, an intermediate aqueous solution containing sodium diethylphosphinate was obtained. (2) Manufacturing of polymer additives The intermediate aqueous solution containing sodium diethylphosphinate produced in step (1) above was diluted with water until the mass concentration of sodium diethylphosphinate in the intermediate aqueous solution was 20%, 500 kg was taken and heated to 40°C, and this was added dropwise to 308.4 kg of a 25% mass aqueous solution of aluminum sulfate 18-hydrate with a pH of 3.0-3.1 to induce a double decomposition reaction (maintaining the pH of 3.0-3.1 and the reaction temperature of 40°C during the reaction), with a dropwise addition time of 120 minutes. After the addition was completed, the mixture was cooled and filtered sequentially, the filtered cake was washed three times with water equal to three times the weight of the filtered cake, and then dried at 120°C until a constant weight was obtained to obtain the polymer additive.

[0074] Example 2 (1) Preparation of an intermediate aqueous solution containing sodium diethylphosphinate. The specific procedure was as follows: (i) 479.6 kg of a 35% sodium hypophosphite monohydrate aqueous solution was added to a jet loop reactor (volume 1000 L) all at once. Ethylene was introduced into the jet loop reactor, and the reaction was carried out continuously while controlling the pressure of the introduced ethylene to 1.2 MPa and the temperature to 105°C. A 20% sodium persulfate aqueous solution, which was used as an initiator, was continuously replenished into the jet loop reactor at a replenishment rate of 4.5 kg / hour. After about 4 hours, when the ethylene pressure stopped decreasing, the reaction was completed, and an intermediate aqueous solution containing sodium diethylphosphinate was obtained. (2) Manufacturing of polymer additives The intermediate aqueous solution containing sodium diethylphosphinate described above was diluted with water until the mass concentration of sodium diethylphosphinate in the intermediate aqueous solution was 24%. 500 kg was taken and heated to 45°C. This was then added dropwise to 462.5 kg of a 20% mass aqueous solution of aluminum sulfate 18-hydrate with a pH of 3.0-3.1 to induce a double decomposition reaction (maintaining a pH of 3.0-3.1 and a reaction temperature of 45°C during the reaction). The dropwise addition time was 180 minutes. After the addition was complete, the mixture was cooled and filtered sequentially. The filtered cake was washed three times with water equal to three times its weight, and then dried at 120°C until it reached a constant weight to obtain the polymer additive.

[0075] Example 3 (1) 318 g of solid sodium hypophosphite monohydrate, 500 g of water, and 3 g of sodium persulfate aqueous solution (mass concentration 20 wt%) were placed in an autoclave, the air in the autoclave was replaced with nitrogen gas, ethylene was introduced into the autoclave and the pressure was kept constant at 1.6 MPa using a vacuum valve, the autoclave was heated to 95°C and the temperature was maintained for 4 hours, during which time the sodium persulfate aqueous solution was continuously replenished, and then the temperature was maintained at 95°C for 1 hour, cooled and evacuated to obtain an intermediate aqueous solution containing diethylphosphinate. (2) The entire intermediate aqueous solution containing diethylphosphinate was diluted with water until the mass concentration of sodium diethylphosphinate in the intermediate aqueous solution was 20%, cooled to 3°C, and added dropwise over 2 hours with stirring to an aluminum sulfate aqueous solution prepared from 333 g of aluminum sulfate 18-hydrate and 1332 g of water at 3°C. After the addition was complete, it was heated to 90°C at a heating rate of 10°C / hour, the temperature was maintained for 10 minutes, filtered, and the filtered cake was washed three times with water equal to three times the weight of the filtered cake, dried to a constant weight, and a polymer additive was obtained.

[0076] Example 4 Example 4 differed from Example 3 in the following respects. In step (2), the intermediate aqueous solution was diluted until the mass concentration of sodium diethylphosphinate in the intermediate aqueous solution was 20%, cooled to 3°C, and added dropwise over 2 hours to an aqueous aluminum sulfate solution prepared from 333 g of aluminum sulfate 18-hydrate and 1332 g of water at 3°C. After the addition was complete, it was heated to 90°C at a heating rate of 5°C / hour, the temperature was maintained for 10 minutes, filtered, the filtered cake was washed three times with water equal to three times the weight of the filtered cake, dried to a constant weight, and a polymer additive was obtained.

[0077] Example 5 (1) 396 kg of a 50% mass hypophosphorous acid aqueous solution was placed in an autoclave, the air inside the autoclave was replaced five times with nitrogen at 0.6 MPa, and ethylene was added until the autoclave pressure reached 1.0 MPa. The autoclave was heated to 80°C while stirring and maintained at that temperature for 3 hours. During this 3-hour temperature maintenance, 40 g of a 10% mass sodium persulfate aqueous solution was continuously added. During the temperature maintenance, the substances inside the autoclave were introduced into the liquid inlet of the Venturi ejector through a valve at the bottom of the autoclave using a centrifugal pump, and ethylene gas from the upper layer of the autoclave was introduced through the gas inlet of the Venturi ejector. Both the gas phase and the liquid phase were thoroughly mixed and entered the autoclave by external circulation. Fresh ethylene was introduced through the gas inlet of the Venturi ejector to replenish the ethylene consumed in the reaction and stabilize the autoclave pressure at 1.0 MPa. After the completion of initiator replenishment, the temperature was maintained for 1 hour, cooled and evacuated to obtain a diethylphosphinic acid aqueous solution. (2) An aqueous sodium hydroxide solution prepared using 60 g of sodium hydroxide and 1140 g of water was slowly added dropwise to an aqueous aluminum sulfate solution prepared from 333 g of aluminum sulfate 18-hydrate and 777 g of water at 15°C over 1.5 hours to obtain an aluminum hydroxide gel. (3) Dilute the diethylphosphinic acid aqueous solution until the mass concentration of diethylphosphinic acid in the diethylphosphinic acid aqueous solution is 25%, take 1464g and dropwise add it to the aluminum hydroxide gel from step (2) over 2 hours, then heat to 115°C at a heating rate of 20°C / hour, maintain the temperature for 1 hour, filter, wash the filtered cake three times with water equal to three times the weight of the filtered cake, dry until it reaches a constant weight, and obtain the polymer additive.

[0078] Example 6 (1) The diethylphosphinic acid aqueous solution from step (1) of Example 5 was collected. (2) At 15°C, an aqueous sodium hydroxide solution prepared from 60 g of sodium hydroxide and 1140 g of water was slowly added dropwise over 1.5 hours to an aqueous aluminum sulfate solution prepared from 333 g of aluminum sulfate 18-hydrate and 777 g of water to obtain an aluminum hydroxide gel. (3) 1464 g of a 25% diethylphosphinic acid aqueous solution from Example 5 was added dropwise to the aluminum hydroxide gel over 2 hours, then the temperature was raised to 115°C at 5°C / hour, the temperature was maintained for 1 hour, the gel was filtered, the filtered cake was washed three times with water equal to three times the weight of the filtered cake, and dried until it reached a constant weight to obtain the polymer additive.

[0079] Comparative Example 1 Conventional polymer additive 1 (BEP-22E, Zhuhai Jin Generating Materials Co., Ltd.) was used.

[0080] Comparative Example 2 Conventional polymer additive 2 (Exolit OP 1230, Clariant) was used.

[0081] Measurement example (1) For the polymer additives produced in Examples 1 to 6 and the polymer additives of Comparative Examples 1 to 2 31 P-NMR spectra were measured. The specific measurements were as follows: (i) Equipment: Nuclear magnetic resonance spectrometer (Bruker 400M). (ii) Reagent: 10% by weight deuterated sulfuric acid aqueous solution. (iii) Experimental method: Approximately 0.1 g (with an accuracy of 0.0001 g) of the test sample was weighed, 5 g of 10 wt% deuterated sulfuric acid aqueous solution was added, and it was dissolved by ultrasound. The solution was transferred to an NMR tube, and the NMR tube was placed in a nuclear magnetic resonance spectrometer and scanned to obtain an NMR spectrum. The integral values ​​were determined for the peaks of aluminum diethylphosphinate and aluminum ethylbutylphosphinate in the NMR spectrum, and the molar percentages of each were obtained. After conversion, the mass percentages of each were determined.

[0082] The measurement results for polymer additives are shown in Table 1 below, expressed as mass percentages.

[0083] Table 1 JPEG2026109605000002.jpg43162

[0084] (2) The polymer additives in each of the above examples and comparative examples were measured by the following method. Differential scanning calorimetry (DSC): Measurements were performed using a differential scanning calorimeter (model: NETZSCH DSC 204 F1). The measured dose of the polymer additive was 10 mg. The polymer additives prepared in each example and the comparative example were heated from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min, maintained at this temperature for 3 minutes, and then cooled back down to room temperature at a further rate of 20°C / min to obtain the cooling curve of the polymer additives. After maintaining the polymer additives at room temperature for 3 minutes, they were again heated to a maximum temperature of 300°C at a heating rate of 20°C / min to obtain the second heating curve of the polymer additives.

[0085] The start and end temperatures of the exothermic peak in the cooling curve were selected, and the peak area formed by these temperatures was calculated as H1 (crystallization enthalpy). The peak temperature of this peak was defined as T1. The start and end temperatures of the endothermic peak in the second heating curve were selected, and the peak area was calculated as H2 (defined as crystal form conversion enthalpy). The peak temperature of this peak was defined as T2. Here, the dual enthalpy ratio ΔH = H2 / H1.

[0086] The peak temperatures and peak areas mentioned above were marked and calculated using the software included with the NETZSCH DSC 204 F1.

[0087] The above measurement results are shown in Table 2 below.

[0088] Table 2 JPEG2026109605000003.jpg80128

[0089] (3) The polymer additives of the above examples and comparative examples were used together with polyphosphate melamine salt (MPP) as a synergistic agent as a flame retardant, and the mixture was kneaded with glass fibers and a base resin and extruded to produce a composite material. The amounts of each component used in Examples 7 to 13 and Comparative Examples 3 to 4 are shown in Table 3.

[0090] Corrosion Performance Test: The degree of corrosion during the process of manufacturing composite materials by kneading and extrusion in the above examples and comparative examples was measured. Specifically, a 20mm x 5mm x 2mm 304L stainless steel metal block (00Cr19Ni11) was placed in the die of a twin-screw extruder with a screw diameter of 20mm and an aspect ratio of 33:1 (a recess the same size as the metal block was made in the lower part of the inside of the die, and the metal block was embedded there). At an injection temperature of 270°C, the high-temperature material was brought into contact with the metal block in the die, and after granulating 50kg of material (feed rate of 5kg / hour), the amount of metal loss (percentage of weight loss) was measured. The greater the amount of loss, the higher the corrosive value and the lower the corrosion resistance. The measurement results for the examples and comparative examples are shown in Table 4 below.

[0091] Table 3 JPEG2026109605000004.jpg66165

[0092] Table 4 JPEG2026109605000005.jpg18166

[0093] From the data of the examples in Table 4, it was found that the composite material containing the polymer additive of the present invention exhibits less metal block loss during mixing and extrusion. This indicates that when the dual enthalpy ratio ΔH and T1, T2 of the polymer additive are within a specific range, the corrosiveness of the polymer additive to the metal block is lower during the flame retardation modification process. The composite material containing the polymer additive of the present invention exhibits a metal loss of ≤0.44 during mixing and extrusion.

[0094] From the Examples, Comparative Example 3, and Comparative Example 4, it can be seen that when the dual enthalpy ratio ΔH of the polymer additive is within a certain range, the composite material containing the polymer additive exhibits lower corrosiveness to the metal block during kneading and extrusion, and the polymer additive can significantly reduce corrosion to the metal parts.

[0095] The embodiments described herein are for illustrative purposes only and are used to illustrate some features of the method of the present invention. The appended claims are intended to cover as broad a range as possible, and the embodiments presented herein are demonstrated by the applicant's actual experimental results. Accordingly, the applicant's intention is that the appended claims are not limited by the selection of embodiments to illustrate the features of the present invention. Certain numerical ranges used in the claims include subranges therewith, and variations within these ranges should be interpreted as being covered by the appended claims as far as possible.

Claims

1. A polymer additive comprising aluminum diethylphosphinate having the structural formula shown in the following formula (I) and aluminum ethylbutylphosphinate having the structural formula shown in the following formula (II), The polymer additive satisfies the dual enthalpy ratio ΔH defined by the following formula (1): 0.92 ≤ ΔH ≤ 1.06, and also satisfies 130°C ≤ T1 ≤ 155°C and 165°C ≤ T2 ≤ 185°C. ΔH=H2 / H1 (1) H1, H2, T1, and T2 were measured by differential scanning calorimetry (DSC), and the measurement method included heating the polymer additive from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min in a nitrogen atmosphere, maintaining this temperature for 3 minutes, then cooling it down to room temperature at a further rate of 20°C / min to obtain the cooling curve of the polymer additive, maintaining the polymer additive at room temperature for 3 minutes, and then heating it again to a maximum temperature of 300°C at a heating rate of 20°C / min to obtain the second heating curve of the polymer additive. H1 is the peak area formed by the start and end temperatures of the exothermic peak in the cooling curve, and T1 is the peak temperature of the exothermic peak in the cooling curve. H2 is the peak area formed by the start and end temperatures of the endothermic peak in the second heating curve, and T2 is the peak temperature of the endothermic peak in the second heating curve. A polymer additive characterized by the following features.

2. The polymer additive according to claim 1, characterized by containing 97.01% to 98.99% by weight of aluminum diethylphosphinate and 1.01% to 2.99% of aluminum ethylbutylphosphinate.

3. The polymer additive according to claim 1, characterized in that the polymer additive satisfies the dual enthalpy ratio ΔH: 0.93 ≤ ΔH ≤ 1.05, and the polymer additive satisfies 132°C ≤ T1 ≤ 153°C and 170°C ≤ T2 ≤ 183°C.

4. A method for producing a polymer additive according to any one of claims 1 to 3, wherein the production method is selected from the first method, the second method, or the third method. Of these, the first method is, Step (a) involves introducing a water-soluble salt or acid of hypophosphorous acid and an initiator into a jet loop reaction system, and reacting the olefin with the acid such that 2.00 to 2.05 molecules of olefin are added to one P atom of the water-soluble salt or acid of hypophosphorous acid itself, thereby obtaining an intermediate aqueous solution containing diethylphosphinate. (b) A step in which an aqueous intermediate solution is subjected to a double decomposition reaction with a water-soluble aluminum salt to obtain a polymer additive, Includes, The second method is, (a) A water-soluble salt or acid of hypophosphorous acid is reacted with an olefin at 90-100°C in the presence of an initiator, under the protection of a nitrogen gas atmosphere, such that 2.00 to 2.05 molecules of olefin are added to each P atom in one water-soluble salt or acid of hypophosphorous acid itself, and the temperature is maintained to obtain an intermediate aqueous solution containing diethylphosphinate. (b) step, while stirring, mix the intermediate aqueous solution and the water-soluble aluminum salt at ≤15°C and allow the reaction to proceed, then raise the temperature to 70-95°C and maintain the temperature to obtain a polymer additive, Includes, The third method is, Step (a) involves reacting hypophosphorous acid with an olefin at 90-100°C under the protection of a nitrogen gas atmosphere, in the presence of an initiator, such that 2.00 to 2.05 molecules of olefin are added to the P atom in the acid itself of one hypophosphorous acid molecule, maintaining the temperature, to obtain an intermediate aqueous solution containing diethylphosphinic acid. Step (b) for producing an aluminum hydroxide gel solution, Step (c) involves adding an intermediate aqueous solution dropwise into an aluminum hydroxide gel solution and allowing it to react, raising the temperature to 90-120°C, and maintaining the temperature for 0.1-5 hours to obtain a polymer additive. including, A manufacturing method characterized by the following features.

5. In step (a) of the first method, the pressure of the olefin in the jet loop reaction system is 0.3 to 3.0 MPa, and / or In step (a) of the first method, the reaction temperature in the jet loop reaction system is 70 to 150°C, and / or In step (b) of the first method, the mass concentration of diethylphosphinate in the aqueous intermediate solution is 20-25%, and / or In step (b) of the first method, the mass concentration of the water-soluble aluminum salt in the water-soluble aluminum salt solution is 20-25%, and / or In step (b) of the first method, the pH of the double decomposition reaction is 3.0 to 3.1, the temperature of the double decomposition reaction is 40 to 45°C, and / or In step (b) of the first or second method, or step (c) of the third method, the molar ratio of diethylphosphinate or diethylphosphinic acid in the aqueous intermediate solution to aluminum ions in the water-soluble aluminum salt is 3:(1 to 1.01). The manufacturing method according to claim 4, characterized in that

6. A corrosion inhibitor comprising a polymer additive according to any one of claims 1 to 3 for reducing corrosion to metal-based production equipment.

7. A flame retardant comprising a polymer additive according to any one of claims 1 to 3, To make at least one of polymers, varnishes, foamed paints, wood, and other cellulose-containing products flame-retardant, as reactive and / or non-reactive. To manufacture flame-retardant polymer molding materials and / or flame-retardant polymer molded articles, and A flame retardant used for at least one of the following: imparting flame retardancy to polyester fabrics and / or pure cellulose fabrics and / or blended cellulose fabrics by impregnation.

8. A flame retardant according to claim 7, wherein the flame retardant is a flame retardant composition, further comprising a synergistic agent, The synergistic agent is one or more selected from the group consisting of melamine phosphate, di(melamine) phosphate, penta(melamine) triphosphate, tri(melamine) diphosphate, tetra(melamine) triphosphate, hexa(melamine) pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, and melon polyphosphate, or The synergistic agent is melamine condensation product, which is melam, melem and / or melon, or The synergistic agent is one or more selected from the group consisting of tri(hydroxyethyl) isocyanurate / salt oligoesters of aromatic polycarboxylic acids, benzoguanamine, tri(hydroxyethyl) isocyanurate / salt, allantoin, glycoluryl, melamine, melamine cyanurate, urea cyanurate, dicyandiamide, and guanidine, or The synergistic agent is given by formula (NH ４ ) ｙ H ３－ｙ PO ４ and / or (NH ４ PO ３ ) ｚ A nitrogen-containing phosphate represented by the formula (where y is 1 to 3 and z is 1 to 10000), or, The synergistic agent is aluminum phosphite and / or aluminum pyrosphite, or The synergistic agent is one or more selected from the group consisting of zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, and magnesium carbonate, or A flame retardant characterized in that the synergistic agent is one or more selected from the group consisting of salts of ethylphosphonic acid, salts of butylphosphonic acid, salts of n-butylphosphonic acid, salts of sec-butylphosphonic acid, and salts of hexylphosphonic acid.

9. A flame retardant according to claim 7, wherein the flame retardant is a flame retardant composition, further comprising other additives, the other additive being at least one selected from the group consisting of antioxidants, UV stabilizers, gamma-ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact resistance modifiers, dyes, and pigments.

10. A flame-retardant thermoplastic or thermosetting polymer composite material, A composite material comprising 0.5 to 45% by weight of a polymer additive according to any one of claims 1 to 3, 0.5 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of a synergistic agent, and 0 to 55% by weight of a filler or reinforcing material.

11. The composite material according to claim 10, wherein the thermoplastic or thermosetting polymer is at least one selected from the group consisting of polyester, polyamide, thermoplastic elastomer, thermoplastic polyurethane, thermoplastic polyester elastomer, styrene polymer, polyketone, polyolefin, and polyacrylate. A composite material characterized by the following features.

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